Substituted hydrazones and fungicides containing these compounds

ABSTRACT

Substituted hydrazones of the formula I   &lt;IMAGE&gt; (I)  where R1, R2 and R3 are hydrogen or alkyl, X (m=1 to 5) is halogen, cyano, trifluoromethyl, nitro, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted phenoxy, substituted or unsubstituted benzyloxy or hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene, carboxymethylene, carbonylamino, methyleneamino or oxygen, and fungicides containing these compounds.

The present invention relates to novel hydrazone derivatives, theirpreparation and their use as fungicides.

It is known that N-tridecyl-2,6-dimethylmorpholine can be used as afungicide (DE-1 164 152). However, its action is inadequate in somecases.

We have found that novel hydrazone derivatives of the formula I ##STR2##where R¹, R² and R³ are identical or different and are each hydrogen oralkyl of 1 to 5 carbon atoms, the radicals X (where m is from 1 to 5)are identical or different substituents from the group consisting ofhalogen, cyano, trifluoromethyl, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,unsubstituted or substituted phenyl, unsubstituted or substitutedphenoxy, unsubstituted or substituted benzyloxy and hydrogen, and Y ismethyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene,carboxymethylene, carbonylamino, methyleneamino or oxygen, not only havea very good fungitoxic action but are also very well tolerated byplants.

Because of the C═N double bond, some of the compounds of the formula Iare obtained in the preparation as E/Z isomer mixtures, which can beseparated into the individual components in a conventional manner, forexample by crystallization or chromatography. The invention embracesboth the individual isomeric compounds and their mixtures.

R¹ and R² are each preferably hydrogen or C₁ -C₅ -alkyl, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,n-pentyl or neopentyl.

R³ is preferably hydrogen or C₁ -C₄ -alkyl, such as methyl, ethyl,isopropyl or n-butyl.

m is preferably 1, 2 or 3.

X is preferably hydrogen, 2-fluoro, 3-fluoro, 4-fluoro,2-chloro-6-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-bromo, 3-bromo,4-bromo, 2,4-dichloro, 2,6-dichloro, 3,5-dichloro, 2,4,6-trichloro,2-chloro-4-methyl, 2-methyl-4-chloro, 2-methyl, 3-methyl, 4-methyl,4-ethyl, 4-isopropyl, 4-tert-butyl, 2,4-dimethyl, 2,6-dimethyl,2,4,6-trimethyl, 2-methoxy-4-methyl, 4-methoxy-2-methyl, 2-methoxy,3-methoxy, 4-methoxy, 4-ethoxy, 4-isopropoxy, 2-trifluoromethyl,3-trifluoromethyl, 4-trifluoromethyl, 2-cyano, 4-cyano, 3-nitro,4-nitro, 4-phenyl, 4-benzyloxy, 4-phenoxy, halophenoxy, such as4-(2-chlorophenoxy) or 4-(2,4-dichlorophenoxy), C₁ -C₄ -alkylphenoxy,such as 4-(2-methyphenoxy), 3-benzyloxy, halobenzyloxy, such as3-(2-chlorobenzyloxy), 3-(2,4-dichlorobenzyloxy), 3-(2-fluorobenzyloxy)or 3-(4-bromobenzyloxy), C₁ -C₄ -alkylbenzyloxy, such as3-(2-methylbenzyloxy), 3-phenoxy, 3-(2-chlorophenoxy),3-(2,4-dichlorophenoxy), 3-(2-fluorophenoxy), 3-(4-bromophenoxy) or3-(2-methylphenoxy), and Y is preferably --CH₂ O--, --OCH₂ --, --CH₂--CH₂ --, --CH═CH--, --C═C--, --CO₂ --CH₂ --, --CO--NH--, --CH₂ --NH--or O.

The novel compounds can be prepared by reacting an α-ketocarboxylicester of the formula II ##STR3## where X_(m), Y and R³ have theabovementioned meanings, with a substituted hydrazine of the generalformula III, where R¹ and R² have the abovementioned meanings ##STR4##in the presence of a protic acid (eg. hydrochloric acid) in a solvent(eg. methanol) (cf. H. Neunhoeffer, M. Neunhoeffer and W. Litzius,Liebigs Ann. Chem. 722 (1969), 29-37).

The α-ketocarboxylic esters of the formula II can be prepared byreacting the corresponding Grignard compounds, for example ##STR5## withimidazolides of the formula IV (J. S. Nimitz and H. S. Mosher, J. Org.Chem. 46 (1981), 211-213) ##STR6## where X, m, Y and R³ have theabovementioned meanings.

Another preparation process for α-ketocarboxylic esters of the formulaII (where Y is --CO--NH-- or --CH₂ --NH) is, for example, the following:

Isatin is reacted with an unsubstituted or substituted benzoyl halide oran unsubstituted or substituted benzyl halide in the presence of a base,for example sodium hydride, in a solvent, for exampleN,N-dimethylformamide, to give an N-substituted isatin of the formula Vor VI (cf. G. Tacconi, P. P. Righetti, G. Desimoni, J. prakt. Chem. 315(1973), 339-334) ##STR7## where X and m have the abovementionedmeanings. Heating in R³ --OH, where R³ has the abovementioned meanings,in the presence of a Lewis acid or protic acid, for example titaniumtetrachloride or HCl, gives the α-ketocarboxylic esters of the formulaII: ##STR8##

Another preparation process for α-ketocarboxylic esters of the formulaII (where Y is --CO₂ --CH₂ --) is, for example, the following:

Methyl α-(2-bromomethylphenyl)-β-methoxyacrylate (cf. DE-3 545 318, DE-3545 319 and DE-3 620 860) in a solvent ##STR9## (eg. methanol) issubjected to ozonolysis (cf. Bailey, Ozonation in Organic Chemistry,Academic Press, N.Y., 1982), and the novel compound methyl2-(bromomethyl)-phenylglyoxylate VII is obtained. This compound is auseful intermediate for the preparation of the novel hydrazones.

By reacting compound VII with a known carboxylate of the formula VIII##STR10## where X and m have the abovementioned meanings and R⁴ is, forexample, sodium or potassium, in a solvent, for exampleN,N-dimethylformamide (cf. Synthesis 1975, 805-807), the novelα-ketocarboxylic esters of the formula II (where Y is --CO₂ --CH₂ --)are obtained.

By reacting compound VII with a phenol derivative of the formula IX (cf.Houben-Weyl, Methoden der organischen Chemie VI/3, 54 et seq. (1965))##STR11## where X and m have the abovementioned meanings, in a solvent(eg. methanol) in the presence of a base, eg. sodium carbonate, theα-ketocarboxylic esters of the formula II (where Y is --OCH₂ --) areobtained.

Another preparation process for methyl 2-(bromomethyl)-phenylglyoxylateVII is, for example, the following:

Bromination of the known α-ketocarboxylic ester of the formula X (cf.for example J. M. Photis, Tetrahedron Lett. 1980, 3539) ##STR12## withbromine in a solvent, eg. tetrachloromethane, with or without exposureto a light source (for example a 300 W mercury vapor lamp) orbromination with N-bromosuccinimide (Horner and Winkelmann, Angew. Chem.71 (1959), 349) leads to the compound VII.

The preparation of the compounds of the formulae I, II and VII isillustrated by the following Examples: 1. Preparation of methyl2-(bromomethyl)-phenylglyoxylate 1.1 2.85 g (10 millimoles) of methylα-(2-bromomethylphenyl)-β-methoxyacrylate are dissolved in 30 ml of 1:1dichloromethane/ethanol at -78° C. Ozone is passed into the stirredsolution for one hour until a pale blue coloration is obtained (ozonegenerator: Fischer OZ 501, 60 l of O₂ /h).

1.24 g (20 millimoles) of dimethyl sulfide are then added, and themixture is allowed to warm up to room temperature (20° C.) overnight.The mixture is then poured onto a 1:1:1 mixture of diethyl ether,n-hexane and water. The organic phase is separated off, dried oversodium sulfate and evaporated down. The abovementioned compound isobtained as a yellow oil.

1.2 5.34 g (30 millimoles) of methyl 2-methylphenylglyoxylate and 5.34 g(30 millimoles) of N-bromosuccinimide in 1,000 ml of tetrachloromethaneare exposed for one hour to a 300 W mercury vapor lamp. Then, theor-ganic phase is washed once with water and 3 times with sodiumbicarbonate solution, dried over sodium sulfate/sodium carbonate andevaporated down, and the crude pro-duct is chromatographed over silicagel using 1:9 methyl tert-butyl ether/n-hexane. 3.8 g (49%) of theabovementioned compound are obtained as a yellow oil.

The compound VII has the following physical properties:

¹ H-NMR (CDCl₃): δ=3.97 (s, 3H), 4.90 (s, 2H), 7.4-7.8 (m, 4H).

IR (film): 2955, 1740, 1689, 1435, 1318, 1207, 999 cm⁻¹.

2. Methyl 2-(benzoylamino)-phenylglyoxylate

2.1 Preparation of N-benzoylisatin.

14.7 g (0.10 mole) of isatin (dissolved in 100 ml ofN,N-dimethylformamide) are added to 2.6 g (0.11 mole) of sodium hydridein 100 ml of N,N-dimethylformamide, while stirring. After the mixturehas been stirred for one hour at room temperature, 14.1 g (0.10 mole) ofbenzoyl chloride are added dropwise at 0° C. Stirring is then continuedfor 10 minutes at 0° C. and the mixture is poured onto ice. Theprecipitate which separates out is filtered off under suction and driedto give 20 g (80%) of N-benzoylisatin as yellow crystals.

IR (film): 2470, 1776, 1746, 1687, 1605, 1465, 1336, 1287, 761.

2.2 Preparation of methyl 2-(benzoylamino)-phenylglyoxylate.

13 g (52 millimoles) of N-benzoylisatin together with one drop ofconcentrated hydrochloric acid in 100 ml of methanol are refluxed foreight hours. After cooling, the mixture is evaporated down in a rotaryevaporator to give 14 g (95%) of the abovementioned α-ketocarboxylicester as yellow crystals having the following physical properties:

¹ H-NMR (CDCl₃): δ=4.03 (s, 3H), 7.22 (m, 1H), 7.55 (m, 3H), 7.76 (m,3H), 8.10 (d, 2H), 9.05 (d, 1H), 12.10 (s, 1H).

IR (film): 3315, 1733, 1647, 1583, 1535, 1450, 1297, 1210, 1159, 694.

3. Preparation of methyl 2-(benzyloxy)-phenylglyoxylate

0.1 mole of a Grignard compound prepared from 1-benzyloxy-2-bromobenzeneand magnesium turnings in tetrahydrofuran is slowly added dropwise to14.6 g (95 millimoles) of methyloxalylimidazole in tetrahydrofuran undernitrogen at -50° C. The mixture is allowed to reach room temperature(20° C.) slowly over a period of 4 hours. It is poured onto ice waterand extracted several times with ether. The combined ether phases arewashed neutral and dried. The solvent is evaporated off and the productis then brought to crystallization with n-pentane. 16 g (62%) ofcolorless crystals of the abovementioned compound were obtained.

¹ H-NMR (CDCl₃): δ=3.35 (s, 3H), 5.07 (s, 2H), 7.05 (m, 2H), 7.40 (m,5H), 7.55 (m, 1H), 7.90 (m, 1H).

4. Preparation of N-methylhydrazone of methyl2-(benzyloxy)-phenylglyoxylate (compound No. 1 in the Table)

13.5 g (50 millimoles) of methyl 2-(benzyloxy)-phenylglyoxylate, 2.3 g(50 millimoles) of methylhydrazine and 25 ml of 2N HCl in 250 ml ofmethanol are stirred for 3 days at room temperature. The mixture isevaporated down, the residue is taken up in ethyl acetate and thesolution is washed with dilute sodium bicarbonate solution and then withwater. It is dried over sodium sulfate and then evaporated down. Thecrude product is chromatographed over a silica gel column (9:1cyclohexane/ethyl acetate). 2.7 g (18%) of the above-mentioned hydrazoneare obtained as a yellow oil.

¹ H-NMR (CDCl₃): δ=3.25 (s, 3H), 3.55 (s, 3H), 5.05 (s, 2H), 6.85-7.05(m, 2H), 7.2-7.4 (m, 6H).

The compounds below can be prepared in a similar manner.

                                      TABLE                                       __________________________________________________________________________     ##STR13##                                       (I)                          Comp.                                                                         no. X.sub.m      Y        R.sup.1                                                                           R.sup.2                                                                          R.sup.3                                                                           M.p.(°C.) IR(cm.sup.-1)           __________________________________________________________________________    1   H            CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                                                          3265, 1671, 1489, 1434,                                                       1320, 1221, 1159, 759                    2   2-F          CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     3   3-F          CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     4   4-F          CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     5   2-Cl, 6-F    CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     6   2-Cl         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                                                          3320, 1681, 1546, 1437,                                                       1327, 1256, 1162, 756                    7   3-Cl         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     8   4-Cl         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     9   2-Br         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     10  3-Br         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     11  4-Br         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     12  2,4-Cl.sub.2 CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     13  2,6-Cl.sub.2 CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     14  3,5-Cl.sub.2 CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     15  2,4,6-Cl.sub.3                                                                             CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     16  2-Cl, 4-CH.sub.3                                                                           CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     17  2-CH.sub.3, 4-Cl                                                                           CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     18  2-CH.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     19  3-CH.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     20  4-CH.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     21  4-C.sub.2 H.sub.5                                                                          CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     22  4-i-C.sub.3 H.sub.7                                                                        CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     23  4-t-C.sub.4 H.sub.9                                                                        CH.sub.2 O                                                                             CH.sub. 3                                                                         H  CH.sub.3                                     24  2,4-(CH.sub.3).sub.2                                                                       CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     25  2,6-(CH.sub.3).sub.2                                                                       CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     26  2,4,6-(CH.sub.3).sub.3                                                                     CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     27  2-OCH.sub.3, 4-CH.sub.3                                                                    CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     28  4-OCH.sub.3, 2-CH.sub.3                                                                    CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     29  2-OCH.sub.3  CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     30  3-OCH.sub.3  CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                                                          113-115; 3315,1675,                                                           1545, 1436, 1328, 1270, 1230,                                                 1160, 1040, 768                          31  4-OCH.sub.3  CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     32  4-OC.sub.2 H.sub.5                                                                         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     33  4-O-i-C.sub. 3 H.sub.7                                                                     CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     34  2-CF.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     35  3-CF.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     36  4-CF.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     37  2-CN         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     38  4-CN         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     39  3-NO.sub.2   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     40  4-NO.sub.2   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     41  4-C.sub.6 H.sub.5                                                                          CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     42  H            OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                                                          3275, 2955, 1673, 1598,                                                       1528, 1496, 1219, 1153, 755              43  2-F          OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     44  3-F          OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     45  4-F          OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     46  2-Cl, 6-F    OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     47  2-Cl         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                                                          3310, 2950, 1707, 1485                                                        1245, 1158, 750                          48  3-Cl         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     49  4-Cl         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     50  2-Br         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     51  3-Br         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     52  4-Br         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     53  2,4-Cl.sub.2 OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     54  2,6-Cl.sub.2 OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     55  3,5-Cl.sub.2 OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     56  2,4,6-Cl.sub.3                                                                             OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     57  2-Cl, 4-CH.sub.3                                                                           OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     58  2-CH.sub.3, 4-Cl                                                                           OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     59  2-CH.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     60  3-CH.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     61  4-CH.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                                                          3320, 2920, 1684, 1508,                                                       1437, 1330, 1233, 1165, 1014, 760        62  4-C.sub.2 H.sub.5                                                                          OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     63  4-i-C.sub.3 H.sub.7                                                                        OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     64  4-t-C.sub.4 H.sub.9                                                                        OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     65  2,4-(CH.sub.3 ).sub.2                                                                      OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     66  2,6-(CH.sub.3).sub.2                                                                       OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     67  2,4,6-(CH.sub.3).sub.3                                                                     OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     68  2-OCH.sub.3, 4-CH.sub.3                                                                    OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     69  4-OCH.sub.3, 2-CH.sub.3                                                                    OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     70  2-OCH.sub.3  OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     71  3-OCH.sub.3  OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     72  4-OCH.sub.3  OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     73  4-OC.sub.2 H.sub.5                                                                         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     74  4-O-iC.sub. 3 H.sub.7                                                                      OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     75  2-CF.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     76  3-CF.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     77  4-CF.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     78  2-CN         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     79  4-CN         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     80  3-NO.sub.2   OCH.sub.2                                                                              CH.sub. 3                                                                         H  CH.sub.3                                     81  4-NO.sub.2   OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     82  4-C.sub.6 H.sub.5                                                                          OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     83  H            CHCH     CH.sub.3                                                                          H  CH.sub.3                                     84  2-F          CHCH     CH.sub.3                                                                          H  CH.sub.3                                     85  3-F          CHCH     CH.sub.3                                                                          H  CH.sub.3                                     86  4-F          CHCH     CH.sub.3                                                                          H  CH.sub.3                                     87  2-Cl, 6-F    CHCH     CH.sub.3                                                                          H  CH.sub.3                                     88  2-Cl         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     89  3-Cl         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     90  4-Cl         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     91  2-Br         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     92  3-Br         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     93  4-Br         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     94  2,4-Cl.sub.2 CHCH     CH.sub.3                                                                          H  CH.sub.3                                     95  2,6-Cl.sub.2 CHCH     CH.sub.3                                                                          H  CH.sub.3                                     96  3,5-Cl.sub.2 CHCH     CH.sub.3                                                                          H  CH.sub.3                                     97  2,4,6-Cl.sub.3                                                                             CHCH     CH.sub.3                                                                          H  CH.sub.3                                     98  2-CH.sub.3, 4-Cl                                                                           CHCH     CH.sub.3                                                                          H  CH.sub.3                                     99  2-Cl, 4-CH.sub.3                                                                           CHCH     CH.sub.3                                                                          H  CH.sub.3                                     100 2-CH.sub.3   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     101 3-CH.sub.3   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     102 4-CH.sub.3   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     103 4-C.sub.2 H.sub.5                                                                          CHCH     CH.sub.3                                                                          H  CH.sub.3                                     104 4-i-C.sub.3 H.sub.7                                                                        CHCH     CH.sub.3                                                                          H  CH.sub.3                                     105 4-t-C.sub.4 H.sub.9                                                                        CHCH     CH.sub.3                                                                          H  CH.sub.3                                     106 2,4-(CH.sub.3).sub.2                                                                       CHCH     CH.sub.3                                                                          H  CH.sub.3                                     107 2,6-(CH.sub.3).sub.2                                                                       CHCH     CH.sub.3                                                                          H  CH.sub.3                                     108 2,4,6-(CH.sub.3).sub.3                                                                     CHCH     CH.sub.3                                                                          H  CH.sub.3                                     109 2-OCH.sub.3, 4-CH.sub.3                                                                    CHCH     CH.sub.3                                                                          H  CH.sub.3                                     110 4-OCH.sub.3, 2-CH.sub.3                                                                    CHCH     CH.sub.3                                                                          H  CH.sub.3                                     111 2-OCH.sub.3  CHCH     CH.sub.3                                                                          H  CH.sub.3                                     112 3-OCH.sub.3  CHCH     CH.sub.3                                                                          H  CH.sub. 3                                    113 4-OCH.sub.3  CHCH     CH.sub.3                                                                          H  CH.sub.3                                     114 4-OC.sub.2 H.sub.5                                                                         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     115 4-O-i-C.sub. 3 H.sub.7                                                                     CHCH     CH.sub.3                                                                          H  CH.sub.3                                     116 2-CF.sub.3   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     117 3-CF.sub.3   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     118 4-CF.sub.3   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     119 2-CN         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     120 4-CN         CHCH     CH.sub.3                                                                          H  CH.sub.3                                     121 3-NO.sub.2   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     122 4-NO.sub.2   CHCH     CH.sub.3                                                                          H  CH.sub.3                                     123 4-C.sub.6 H.sub.5                                                                          CHCH     CH.sub.3                                                                          H  CH.sub.3                                     124 H            CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     125 2-F          CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     126 3-F          CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     127 4-F          CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     128 2-Cl, 6-F    CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     129 2-Cl         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     130 3-Cl         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     131 4-Cl         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     132 2-Br         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     133 3-Br         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     134 4-Br         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     135 2,4-Cl.sub.2 CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     136 2,6-Cl.sub.2 CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     137 3,5-Cl.sub.2 CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     138 2,4,6-Cl.sub.3                                                                             CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     139 2-Cl, 4-CH.sub.3                                                                           CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     140 2-CH.sub.3, 4-Cl                                                                           CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     141 2-CH.sub.3   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     142 3-CH.sub.3   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     143 4-CH.sub.3    CH.sub.2CH.sub.2                                                                      CH.sub.3                                                                          H  CH.sub.3                                     144 4-C.sub.2 H.sub.5                                                                          CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     145 4-i-C.sub.3 H.sub.7                                                                        CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     146 4-t-C.sub.4 H.sub.9                                                                        CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     147 2,4-(CH.sub.3).sub.2                                                                       CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     148 2,6-(CH.sub.3).sub.2                                                                       CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     149 2,4,6-(CH.sub.3).sub.3                                                                     CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     150 2-OCH.sub.3, 4-CH.sub.3                                                                    CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     151 4-OCH.sub.3, 2-CH.sub.3                                                                    CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     152 2-OCH.sub.3  CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     153 3-OCH.sub.3  CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     154 4-OCH.sub.3  CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     155 4-OC.sub.2 H.sub.5                                                                         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     156 4-O-i-C.sub.3 H.sub.7                                                                      CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     157 2-CF.sub.3   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     158 3-CF.sub.3   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     159 4-CF.sub.3   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     160 2-CN         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     161 4-CN         CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     162 3-NO.sub.2   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     163 4-NO.sub.2   CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     164 4-C.sub.6 H.sub.5                                                                          CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     165 H            ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     166 2-F          ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     167 2-Cl         ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     168 2-Br         ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     169 4-Br         ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     170 2-CH.sub.3   ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     171 4-CH.sub.3   ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     172 2-OCH.sub.3  ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     173 4-CF.sub.3   ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     174 2-NO.sub.2   ethynylene                                                                             CH.sub.3                                                                          H  CH.sub.3                                     175 H            O        CH.sub.3                                                                          H  CH.sub.3                                     176 2-F          O        CH.sub.3                                                                          H  CH.sub.3                                     177 2-Cl         O        CH.sub.3                                                                          H  CH.sub.3                                     178 2-Br         O        CH.sub.3                                                                          H  CH.sub.3                                     179 4-Br         O        CH.sub.3                                                                          H  CH.sub.3                                     180 4-Cl         O        CH.sub.3                                                                          H  CH.sub.3                                     181 2-CH.sub.3   O        CH.sub.3                                                                          H  CH.sub.3                                     182 4-CH.sub.3   O        CH.sub.3                                                                          H  CH.sub.3                                     183 2-OCH.sub.3  O        CH.sub.3                                                                          H  CH.sub.3                                     184 4-OCH.sub.3  O        CH.sub.3                                                                          H  CH.sub.3                                     185 4-C.sub.6 H.sub.5                                                                          O        CH.sub.3                                                                          H  CH.sub.3                                     186 H            CH.sub.2 O                                                                             H   H  H                                            187 H            OCH.sub.2                                                                              H   H  H                                            188 4-OCH.sub.2C.sub.6 H.sub.5                                                                 CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     189 4-OCH.sub.2C.sub.6 H.sub.5                                                                 OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     190 4-OC.sub.6 H.sub.5                                                                         CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     191 4-OC.sub.6 H.sub.5                                                                         OCH.sub.2                                                                              CH.sub.3                                                                          H  CH.sub.3                                     192                                                                                ##STR14##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     193                                                                                ##STR15##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     194                                                                                ##STR16##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     195 3-OCH.sub.2C.sub.6 H.sub.5                                                                 CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     196                                                                                ##STR17##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     197                                                                                ##STR18##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     198                                                                                ##STR19##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     199                                                                                ##STR20##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     200                                                                                ##STR21##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     201 3-OC.sub. 6 H.sub.5                                                                        CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     202                                                                                ##STR22##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     203                                                                                ##STR23##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     204                                                                                ##STR24##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     205                                                                                ##STR25##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     206                                                                                ##STR26##   CH.sub.2 O                                                                             CH.sub.3                                                                          H  CH.sub.3                                     207 H            CH.sub.2 O                                                                             CH.sub.3                                                                          H  H                                            208 H            CH.sub.2 O                                                                             CH.sub.3                                                                          H  C.sub.2 H.sub.5                              209 H            CH.sub.2 O                                                                             CH.sub.3                                                                          H  C.sub.3 H.sub.7                              210 H            CH.sub.2 O                                                                             CH.sub.3                                                                          H  i-C.sub.3 H.sub.7                            211 H            CH.sub.2 O                                                                             CH.sub.3                                                                          H  n-C.sub.4 H.sub.9                            212 H            OCH.sub. 2                                                                             CH.sub.3                                                                          H  H                                            213 H            OCH.sub.2                                                                              CH.sub.3                                                                          H  C.sub.2 H.sub.5                              214 H            OCH.sub.2                                                                              CH.sub.3                                                                          H  i-C.sub.3 H.sub.7                            215 H            OCH.sub.2                                                                              CH.sub.3                                                                          H  n-C.sub.4 H.sub.9                            216 H            CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     217 2-F          CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     218 3-F          CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     219 4-F          CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     220 2-Cl, 6-F    CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     221 2-Cl         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                          2945, 1693, 1556, 1488, 1437,                                                 1303, 1202, 1072, 1030, 752              222 3-Cl         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     223 4-Cl         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     224 2-Br         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     225 3-Br         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     226 4-Br         CH.sub.2 O                                                                             CH.sub. 3                                                                         CH.sub.3                                                                         CH.sub.3                                     227 2,4-Cl.sub.2 CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     228 2,6-Cl.sub.2 CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     229 3,5-Cl.sub.2 CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     230 2,4,6-Cl.sub.3                                                                             CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     231 2-Cl, 4-CH.sub.3                                                                           CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     232 2-CH.sub.3, 4-Cl                                                                           CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     233 2-CH.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     234 3-CH.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     235 4-CH.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     236 4-C.sub.2 H.sub.5                                                                          CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     237 4-i-C.sub.3 H.sub.7                                                                        CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     238 4-t-C.sub.4 H.sub.9                                                                        CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     239 2,4-(CH.sub.3).sub.2                                                                       CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     240 2,6-(CH.sub. 3).sub.2                                                                      CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     241 2,4,6-(CH.sub.3).sub.3                                                                     CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     242 2-OCH.sub.3, 4-CH.sub.3                                                                    CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     243 4-OCH.sub.3, 2-CH.sub.3                                                                    CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     244 2-OCH.sub.3  CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     245 3-OCH.sub.3  CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     246 4-OCH.sub.3  CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     247 4-OC.sub.2 H.sub.5                                                                         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     248 4-O-i-C.sub. 3 H.sub.7                                                                     CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     249 2-CF.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     250 3-CF.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     251 4-CF.sub.3   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     252 2-CN         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     253 4-CN         CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     254 3-NO.sub.2   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     255 4-NO.sub.2   CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     256 4-C.sub.6 H.sub.5                                                                          CH.sub.2 O                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     257 H            OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     258 2-F          OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     259 3-F          OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     260 4-F          OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     261 2-Cl, 6-F    OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     262 2-Cl         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     263 3-Cl         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     264 4-Cl         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                          2930, 1682, 1554, 1490, 1231,                                                 1209, 1073, 1026, 824                    265 2-Br         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     266 3-Br         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     267 4-Br         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     268 2,4-Cl.sub.2 OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     269 2,6-Cl.sub.2 OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     270 3,5-Cl.sub.2 OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     271 2,4,6-Cl.sub.3                                                                             OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     272 2-Cl, 4-CH.sub.3                                                                           OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     273 2-CH.sub.3, 4-Cl                                                                           OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     274 2-CH.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     275 3-CH.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     276 4-CH.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                                                          3420, 2950, 1681, 1555, 1507,                                                 1438, 1303, 1223, 1026, 813              277 4-C.sub.2 H.sub.5                                                                          OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     278 4-i-C.sub.3 H.sub.7                                                                        OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     279 4-t-C.sub.4 H.sub.9                                                                        OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     280 2,4-(CH.sub.3).sub.2                                                                       OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     281 2,6-(CH.sub.3).sub.2                                                                       OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     282 2,4,6-(CH.sub.3).sub.3                                                                     OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     283 2-OCH.sub.3, 4-CH.sub.3                                                                    OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     284 4-OCH.sub.3, 2-CH.sub.3                                                                    OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     285 2-OCH.sub.3  OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     286 3-OCH.sub.3  OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     287 4-OCH.sub.3  OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     288 4-OC.sub.2 H.sub.5                                                                         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     289 4-O-iC.sub. 3 H.sub.7                                                                      OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     290 2-CF.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     291 3-CF.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     292 4-CF.sub.3   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     293 2-CN         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     294 4-CN         OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     295 3-NO.sub.2   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub. 3                                                                        CH.sub.3                                     296 4-NO.sub.2   OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     297 4-C.sub.6 H.sub.5                                                                          OCH.sub.2                                                                              CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     298 H            CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     299 2-F          CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     300 3-F          CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     301 4-F          CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     302 2-Cl, 6-F    CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     303 2-Cl         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     304 3-Cl         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     305 4-Cl         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     306 2-Br         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     307 3-Br         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     308 4-Br         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     309 2,4-Cl.sub.2 CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     310 2,6-Cl.sub.2 CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     311 3,5-Cl.sub.2 CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     312 2,4,6-Cl.sub.3                                                                             CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     313 2-Cl, 4-CH.sub.3                                                                           CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     314 2-CH.sub.3, 4-Cl                                                                           CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     315 2-CH.sub.3   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     316 3-CH.sub.3   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     317 4-CH.sub.3   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     318 4-C.sub.2 H.sub.5                                                                          CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     319 4-i-C.sub.3 H.sub.7                                                                        CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     320 4-t-C.sub.4 H.sub.9                                                                        CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     321 2,4-(CH.sub.3).sub.2                                                                       CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     322 2,6-(CH.sub.3).sub.2                                                                       CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     323 2,4,6-(CH.sub.3).sub.3                                                                     CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     324 2-OCH.sub.3, 4-CH.sub.3                                                                    CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     325 4-OCH.sub.3, 2-CH.sub.3                                                                    CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     326 2-OCH.sub.3  CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     327 3-OCH.sub.3  CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     328 4-OCH.sub.3  CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     329 4-OC.sub.2 H.sub.5                                                                         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     330 4-O-i-C.sub. 3 H.sub.7                                                                     CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     331 2-CF.sub.3   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     332 3-CF.sub.3   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     333 4-CF.sub.3   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     334 2-CN         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     335 4-CN         CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     336 3-NO.sub.2   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     337 4-NO.sub.2   CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     338 4-C.sub.6 H.sub.5                                                                          CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          H  CH.sub.3                                     339 H            CHCH     CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     340 H            CH.sub.2CH.sub.2                                                                       CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     341 H            ethynylene                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     342 H            O        CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     343 H            CO.sub.2CH.sub.2                                                                       CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     344 H            CH.sub.2 O                                                                             C.sub.2 H.sub.5                                                                   H  CH.sub.3                                     345 H            CH.sub.2 O                                                                             C.sub.3 H.sub.7                                                                   H  CH.sub.3                                     346 H            CH.sub.2 O                                                                             i-C.sub.3 H.sub.7                                                                 H  CH.sub.3                                     347 H            CH.sub.2 O                                                                             n-C.sub.4 H.sub.9                                                                 H  CH.sub.3                                     348 H            CH.sub.2 O                                                                             i-C.sub.4 H.sub.9                                                                 H  CH.sub.3                                     349 H            CH.sub.2 O                                                                             t-C.sub.4 H.sub.9                                                                 H  CH.sub.3                                     350 H            CH.sub.2 O                                                                             C.sub.5 H.sub.11                                                                  H  CH.sub.3                                     351 H            OCH.sub.2                                                                              C.sub.2 H.sub.5                                                                   H  CH.sub.3                                     352 H            OCH.sub.2                                                                              C.sub.3 H.sub.7                                                                   H  CH.sub.3                                     353 H            OCH.sub.2                                                                              i-C.sub.3 H.sub.7                                                                 H  CH.sub.3                                     354 H            OCH.sub.2                                                                              n-C.sub.4 H.sub.9                                                                 H  CH.sub.3                                     355 H            OCH.sub.2                                                                              i-C.sub.4 H.sub.9                                                                 H  CH.sub.3                                     356 H            OCH.sub.2                                                                              t-C.sub.4 H.sub.9                                                                 H  CH.sub.3                                     357 H            OCH.sub.2                                                                              C.sub.5 H.sub.11                                                                  H  CH.sub.3                                     358 H            CH.sub.2 O                                                                             C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                  CH.sub.3                                     359 H            CO.sub.2CH.sub.2                                                                       C.sub.2 H.sub.5                                                                   H  CH.sub.3                                     360 H            CO.sub.2CH.sub.2                                                                       C.sub.3 H.sub.7                                                                   H  CH.sub.3                                     361 H            CONH     CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     362 H            CH.sub.2NH                                                                             CH.sub.3                                                                          CH.sub.3                                                                         CH.sub.3                                     363 H            CONH     C.sub.2 H.sub.5                                                                   H  CH.sub.3                                     364 H            CH.sub.2NH                                                                             C.sub.2 H.sub.5                                                                   H  CH.sub.3                                     365 H            CONH     CH.sub.3                                                                          H  CH.sub.3                                     366 2-F          CONH     CH.sub.3                                                                          H  CH.sub.3                                     367 3-F          CONH     CH.sub.3                                                                          H  CH.sub.3                                     368 4-F          CONH     CH.sub.3                                                                          H  CH.sub.3                                     369 2-Cl, 6-F    CONH     CH.sub.3                                                                          H  CH.sub.3                                     370 2-Cl         CONH     CH.sub.3                                                                          H  CH.sub.3                                     371 3-Cl         CONH     CH.sub.3                                                                          H  CH.sub.3                                     372 4-Cl         CONH     CH.sub.3                                                                          H  CH.sub.3                                     373 2-Br         CONH     CH.sub.3                                                                          H  CH.sub.3                                     374 3-Br         CONH     CH.sub.3                                                                          H  CH.sub.3                                     375 4-Br         CONH     CH.sub.3                                                                          H  CH.sub.3                                     376 2,4-Cl.sub.2 CONH     CH.sub.3                                                                          H  CH.sub.3                                     377 2,6-Cl.sub.2 CONH     CH.sub.3                                                                          H  CH.sub.3                                     378 3,5-Cl.sub.2 CONH     CH.sub.3                                                                          H  CH.sub.3                                     379 2,4,6-Cl.sub.3                                                                             CONH     CH.sub.3                                                                          H  CH.sub.3                                     380 2-Cl, 4-CH.sub.3                                                                           CONH     CH.sub.3                                                                          H  CH.sub.3                                     381 2-CH.sub.3, 4-Cl                                                                           CONH     CH.sub.3                                                                          H  CH.sub.3                                     382 2-CH.sub.3   CONH     CH.sub.3                                                                          H  CH.sub.3                                     383 3-CH.sub.3   CONH     CH.sub.3                                                                          H  CH.sub.3                                     384 4-CH.sub.3   CONH     CH.sub.3                                                                          H  CH.sub.3                                     385 4-C.sub.2 H.sub.5                                                                          CONH     CH.sub.3                                                                          H  CH.sub.3                                     386 4-i-C.sub.3 H.sub.7                                                                        CONH     CH.sub.3                                                                          H  CH.sub.3                                     387 4-t-C.sub.4 H.sub.9                                                                        CONH     CH.sub.3                                                                          H  CH.sub.3                                     388 2,4-(CH.sub.3).sub.2                                                                       CONH     CH.sub.3                                                                          H  CH.sub.3                                     389 2,6-(CH.sub.3).sub.2                                                                       CONH     CH.sub.3                                                                          H  CH.sub.3                                     390 2,4,6-(CH.sub.3).sub.3                                                                     CONH     CH.sub.3                                                                          H  CH.sub.3                                     391 2-OCH.sub.3, 4-CH.sub.3                                                                    CONH     CH.sub.3                                                                          H  CH.sub.3                                     392 4-OCH.sub.3, 2-CH.sub.3                                                                    CONH     CH.sub.3                                                                          H  CH.sub.3                                     393 2-OCH.sub.3  CONH     CH.sub.3                                                                          H  CH.sub.3                                     394 3-OCH.sub.3  CONH     CH.sub.3                                                                          H  CH.sub.3                                     395 4-OCH.sub.3  CONH     CH.sub.3                                                                          H  CH.sub.3                                     396 4-OC.sub.2 H.sub.5                                                                         CONH     CH.sub.3                                                                          H  CH.sub.3                                     397 4-O-i-C.sub.3 H.sub.7                                                                      CONH     CH.sub.3                                                                          H  CH.sub.3                                     398 2-CF.sub.3   CONH     CH.sub.3                                                                          H  CH.sub.3                                     399 3-CF.sub.3   CONH     CH.sub.3                                                                          H  CH.sub.3                                     400 4-CF.sub.3   CONH     CH.sub.3                                                                          H  CH.sub.3                                     401 2-CN         CONH     CH.sub.3                                                                          H  CH.sub.3                                     402 4-CN         CONH     CH.sub.3                                                                          H  CH.sub.3                                     403 3-NO.sub.2   CONH     CH.sub.3                                                                          H  CH.sub.3                                     404 4-NO.sub.2   CONH     CH.sub.3                                                                          H  CH.sub.3                                     405 4-C.sub.6 H.sub.5                                                                          CONH     CH.sub.3                                                                          H  CH.sub.3                                     406 H            CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     407 2-F          CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     408 3-F          CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     409 4-F          CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     410 2-Cl, 6-F    CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     411 2-Cl         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     412 3-Cl         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     413 4-Cl         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     414 2-Br         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     415 3-Br         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     416 4-Br         CH.sub.2 NH                                                                            CH.sub.3                                                                          H  CH.sub.3                                     417 2,4-Cl.sub.2 CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     418 2,6-Cl.sub.2 CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     419 3,5-Cl.sub.2 CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     420 2,4,6-Cl.sub.3                                                                             CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     421 2-Cl, 4-CH.sub.3                                                                           CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     422 2-CH.sub.3, 4-Cl                                                                           CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     423 2-CH.sub.3   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     424 3-CH.sub.3   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     425 4-CH.sub.3   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     426 4-C.sub.2 H.sub.5                                                                          CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     427 4-i-C.sub.3 H.sub.7                                                                        CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     428 4-t-C.sub.4 H.sub.9                                                                        CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     429 2,4-(CH.sub.3).sub.2                                                                       CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     430 2,6-(CH.sub.3).sub.2                                                                       CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     431 2,4,6-(CH.sub.3).sub.3                                                                     CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     432 2-OCH.sub.3, 4-CH.sub.3                                                                    CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     433 4-OCH.sub.3, 2-CH.sub.3                                                                    CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     434 2-OCH.sub.3  CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     435 3-OCH.sub.3  CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     436 4-OCH.sub.3  CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     437 4-OC.sub.2 H.sub.5                                                                         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     438 4-O-i-C.sub. 3 H.sub.7                                                                     CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     439 2-CF.sub.3   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     440 3-CF.sub.3   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     441 4-CF.sub.3   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     442 2-CN         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     443 4-CN         CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     444 3-NO.sub.2   CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     445 4-NO.sub.2   CH.sub. 2NH                                                                            CH.sub.3                                                                          H  CH.sub.3                                     446 4-C.sub.6 H.sub.5                                                                          CH.sub.2NH                                                                             CH.sub.3                                                                          H  CH.sub.3                                     447 2-Cl         CH.sub.2 O                                                                             H   H  CH.sub.3                                                                          3418, 3295, 1718, 1565, 1491,                                                 1435, 1340, 1226, 1029,                  __________________________________________________________________________                                         749                                  

In general terms, the novel compounds are extremely effective on a broadspectrum of phytopathogenic fungi, in particular those from the classconsisting of the Ascomycetes and Basidiomycetes. Some of them have asystemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The compounds are applied by spraying or dusting the plants with theactive ingredients, or treating the seeds of the plants with the activeingredients. They may be applied before or after infection of the plantsor seeds by the fungi.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin, sulfitewaste liquors and methylcellulose.

The fungicides generally contain from 0.1 to 95, and preferably from 0.5to 90, wt % of active ingredient. The application rates are from 0.02 to3 kg or more of active ingredient per hectare, depending on the type ofeffect desired. The novel compounds may also be used for protectingmaterials, e.g., on Paecilomyces variotii.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 30 is mixed with 10 parts byweight of N-methyl-α-pyrrolidone. A mixture is obtained which issuitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 42 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into water and uniformly distributing it therein, an aqueousdispersion is obtained.

III. 20 parts by weight of compound no. 30 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil. By pouring the solution into water andfinely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 42 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanol, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into water and uniformlydistributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 30 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10parts by weight of the sodium salt of a lignin-sulfonic acid obtainedfrom a sulfite waste liquor, and 7 parts by weight of powdered silicagel, and triturated in a hammer mill. By uniformly distributing themixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 42 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 30 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 40 parts by weight of compound no. 422a is intimately mixed with10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehydecondensate, 2 parts of silica gel and 48 parts of water to give a stableaqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 30 is intimately mixed with 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil. A stable oilydispersion is obtained.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in a greater fungicidal actionspectrum.

The following list of fungicides with which the novel compounds may becombined is intended to illustrate possible combinations but not toimpose any restrictions.

Examples of fungicides which may be combined with the novel compoundsare:

sulfur,

dithiocarbamates and their derivatives, such as

ferric dimethyldithiocarbamate,

zinc dimethyldithiocarbamate,

zinc ethylenebisdithiocarbamate,

manganese ethylenebisdithiocarbamate,

manganese zinc ethylenediaminebisdithiocarbamate,

tetramethylthiuram disulfides,

ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,

ammonia complex of zinc N,N'-propylenebisdithiocarbamate,

zinc N,N'-propylenebisdithiocarbamate and

N,N'-polypropylenebis(thiocarbamyl) disulfide;

nitro derivatives, such as

dinitro(1-methylheptyl)-phenyl crotonate,

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and

diisopropyl 5-nitroisophthalate;

heterocyclic substances, such as

2-heptadecylimidazol-2-yl acetate,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

O,O-diethyl phthalimidophosphonothioate,

5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio[4,5-b]quinoxaline,

methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,

2-methoxycarbonylaminobenzimidazole,

2-(fur-2-yl)-benzimidazole,

2-(thiazol-4-yl)benzimidazole,

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,

N-trichloromethylthiotetrahydrophthalimide,

N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-thiocyanatomethylthiobenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene,

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,

2-thiopyridine 1-oxide,

8-hydroxyquinoline and its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,

2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,

2-methylfuran-3-carboxanilide,

2,5-dimethylfuran-3-carboxanilide,

2,4,5-trimethylfuran-3-carboxanilide,

2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,

N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,

2-methylbenzanilide,

2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethylacetal,

piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine,

1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole

1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,

1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,

5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,

bis-(p-chlorophenyl)-3-pyridinemethanol,

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,

1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,

and various fungicides, such as

dodecylguanidine acetate,

3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide,

hexachlorobenzene,

DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate,

methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate,

N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,

5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,

3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,

1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,

2,4-difluoro-α-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,and

1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.

USE EXAMPLES

For comparison purposes, N-tridecyl-2,6-dimethylmorpholine (A) disclosedin DE-1,164,152 was used.

USE EXAMPLE 1 Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 5 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants were then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results show that active ingredients 30 and 42, applied as 0.05%spray liquors, have a better fungicidal action (90%) than prior artcomparative agent A (50%).

USE EXAMPLE 2 Action on Pyricularia oryzae (protective)

Leaves of pot-grown rice seedlings of the "Bahia" variety were sprayedto runoff with aqueous emulsions containing (dry basis) 80% of activeingredient and 20% of emulsifier, and inoculated 24 hours later with anaqueous spore suspension of Pyricularia oryzae. The plants were then setup in climatic cabinets at 22° to 24° C. and 95 to 99% relativehumidity. The extent of fungus attack was assessed after 6 days.

The results show that active ingredient 42, applied as a 0.05% sprayliquor, has a better fungicidal action (90%) than prior art comparativeagent A (50%).

We claim:
 1. Substituted hydrazones of the formula I ##STR27## where R¹, R² and R³ are identical or different and each denotes hydrogen or alkyl of 1 to 5 carbon atoms,X (m=1 to 5) is one or more identical or different substituents selected from the group consisting of halogen, cyano, trifluoromethyl, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, phenoxy, halophenoxy, C₁ -C₄ alkylphenoxy, benzyloxy, halobenzyloxy, C₁ -C₄ -alkylbenzyloxy, and hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene, carboxymethylene, carbonylamino, methyleneamino or oxygen.
 2. Compounds of the formula I as set forth in claim 1, whereX is hydrogen, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro-6-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-bromo, 3-bromo, 4-bromo, 2,4-dichloro, 2,6-dichloro, 3,5-dichloro, 2,4,6-trichloro, 2-chloro-4-methyl, 2-methyl-4-chloro, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-isopropyl, 4-tert-butyl, 2,4-dimethyl, 2,6-dimethyl, 2,4,6-trimethyl, 2-methoxy-4-methyl, 4-methoxy-2-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 4-ethoxy, 4-isopropoxy, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-cyano, 4-cyano, 3-nitro, 4-nitro, 4-phenyl, 4-benzyloxy, 4-phenoxy, halophenoxy, 4-(2-chloro)-phenoxy, 4-(2,4-dichloro)-phenoxy, C₁ -C₄ -alkylphenoxy, 4-(2-methyl)-phenoxy, 3-benzyloxy, halobenzyloxy, 3-(2-chlor)-benzyloxy, 3-(2,4-dichloro)-benzyloxy, 3-(2-fluoro)-benzyloxy, 3-(4-bromo)-benzyloxy, C₁ -C₄ -alkylbenzyloxy, 3-(2-methyl)-benzyloxy, 3-phenoxy, 3-(2-chloro)-phenoxy, 3-(2,4-dichloro)-phenoxy, 3-(2-fluoro)-phenoxy, 3-(4-bromo)-phenoxy, or 3-(2-methyl)-phenoxy, R¹ is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl or neopentyl, R² is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl or neopentyl, R³ is hydrogen, methyl, ethyl, isopropyl, n-butyl and Y is a --CH₂ O--, --OCH₂ --, --CH₂ --CH₂ --, --CH═CH--, --C.tbd.C--, --CO₂ --CH₂ --, --CO--NH--, or --CH₂ --NH-- group or oxygen.
 3. A fungicidal agent containing a substituted hydrazone of the formula I ##STR28## where R¹, R² and R³ are identical or different and each denotes hydrogen or alkyl of 1 to 5 carbon atoms,X (m=1 to 5) is one or more identical or different substituents selected from the group consisting of halogen, cyano, trifluoromethyl, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenyl, phenoxy, halophenoxy, C₁ -C₄ -alkylphenoxy, benzyloxy, halobenzyloxy, C₁ -C₄ -alkylbenzyloxy, and hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene, carboxymethylene, carbonylamino, methyleneamino or oxygen.
 4. A compound as set forth in claim 1, where R¹ is methyl, R² is hydrogen, R³ is methyl, X_(m) is hydrogen and Y is methyleneoxy.
 5. A compound as set forth in claim 1, where R¹ is methyl, R² is hydrogen, R³ is methyl, X_(m) is hydrogen and Y is oxymethylene.
 6. A compound as set forth in claim 1, where R¹ is methyl, R² is hydrogen, R³ is methyl, X_(m) is 3-methoxy and Y is methyleneoxy.
 7. A compound as set forth in claim 1, where R¹ is methyl, R² is methyl, R³ is methyl, X_(m) is 4-methyl and Y is oxymethylene.
 8. A compound as set forth in claim 1, where R¹ and R³ are methyl, R² is hydrogen, X_(m) is 2-methyl and Y is oxymethylene. 